Difluoropyrimidylamino-group-containing metallized water-soluble reactive formazane dyes

ABSTRACT

Metal complexes of reactive water-soluble formazane dyes which contain 2, 3 or 4 sulfonic acid groups and one difluoropyrimidylamino group yield dyeings which have good fastness to light, washing, milling and perspiration.

Q ilmted States Patent 1 1 Grandjean [4 1 Apr. 3, 1973 [54]DIFLUOROPYRIMIDYLAMINO- [56] References Cited GROUP-CONTAiNINGMETALLIZED UNITED STATES PATENTS EACTIVE 3,041,328 6/1962 Kraus et a1..260/ 146 D 3,068,219 12/1962 Beffa et a]. 260/146 D [75] Inventor:Philippe Grandjean, Basel, Switzer- 3,244,690 1966 60/146 D land3,202,649 8/1965 Steinemann.... ..260/146 D 3,202,650 8/1965 Steinemann..260/146 D [7 3] Assignee: Sandoz Ltd., Basel, Switzerland FOREIGNPATENTS OR APPLICATIONS [22] Filed: Mar. 26, 1970 1,330,585 5/1963France ..260/153 [21] App1.No.: 23,024

Primary Examiner-Floyd D. Higel [30] Foreign A fi ti p i DataAttorney-Gera1d D. Sharkin, Thomas C. Doyle,

V 7 l Robert S. Honor, Walter F. Jewell; Thomas 0. Mc- Mar. 26, 1969Sw1tzerland ..4656/69 Govern Richard Vila and Frederick w inf ldt Apr.1, 1969 Switzerland ..4927/69 1 [57] ABSTRACT [52] US. Cl. ..260/146 D,8/10, 8/42 R,

260/149, 260/154 260/193 Metal complexes of react1ve water-so1ubleformazane [51] Int Cl. "mC09b 45/18 C09b62l24 Dop H38 dyes which contain2, 3 or 4 sulfonic acid groups and 58 Field of Search ..260/146 D, 146T, 153, 154 diflwmPYimidylamino Yield dyeings which have good 'fastnessto light, washing, milling and perspiration.

5 Claims, No Drawings DIFLUOROPYRIMIDYLAMINO-GROUP- CONTAININGMETALLIZED WATER-SOLUBLE REACTIVE FORMAZANE DYES This invention relatesto a process for the production of reactive, water-soluble metal complexcompounds which, in the metal-free state, have the formula where Xstands for a hydrogen, chlorine, bromine or fluorine atom or for a loweralkyl group which may be substituted,

Y for hydrogen or a group Z for a lower alkyl group which may besubstituted or an amino group which may be monosubstituted,

n for 2, 3 or 4,

p for l, 2 or 3,

where the sum ofn and p is 3, 4 or 5,

R, and R each stands for a benzene or naphthalene radical which bearsthe OH group in ortho position to -N= or -Nl-l and may be substituted,

R for a hydrogen atom or for an aliphatic radical which may besubstituted,

R for an aliphatic or cycloaliphatic, radical which may be substitutedor for a benzene or naphthalene radical which may be substituted,

or R and R jointly with the adjacent N atom, form a heterocyclic ring.Copper complex compounds which, in the copper-free state, conform to thegeneral formula (l), where X stands for chlorine,

n for 2 or 3,

p for 1 and R and R for benzene or toluene radicals which bear the OHgroup in ortho position to 'N= or NH-, are dyes of notably good quality.

The process of this invention consists of reacting l mole of metalcomplex ofa compound of the formula with 1 mole ofapolyfluoropyrim'idine of the formula (III) The metal complexes of thecompounds of formula (ll) which are used as starting materials in theprocess can be produced by the methods described in French Pat.1,330,585 and British Pat. 1,022,043.

The lower, optionally substituted, alkyl or alkoxy groups may be, e.g.,alkyl or alkoxy groups having one to five carbon atoms. They may bestraight or branched and may bear substituents, such as hydroxyl orlower alkoxy groups (-OCH ,OC H

If the radical Z represents a monosubstituted amino group, thesubstituent at the amino group is a lower alkyl radical which may bearsubstituents, such 1 as hydroxyl and lower alkoxy groups, or the phenylradical which may bear carboxylic or sulfonic acid groups. Suitablegroups of formula SO -Z are, for example,

, lower alkylsulfonyl groups (SO CH -SO C H SO CH(CH and sulfonamidegroups which may be monosubstituted, such as SO NH -SO NHCH SO NHC H OCHSO NHC H och SO NHC H The radicals R and R and likewise the radical R ifit is aromatic, may bear substituents, such as lower alkyl groups(methyl, ethyl), lower alkoxy groups (methoxy, ethoxy), halogen atoms(chlorine, bromine, fluorine), the nitro group, the carboxyl group andacylamino groups, such as lower alkyl carbonylamino, lower alkoxycarbonylamino, aryl carbonylamino groups (acetylamino, propionylamino,butyrylamino, methoxycarbonylamino, ethoxycarbonylamino, benzoylamino).

If the radical R represents optionally substituted alkyl or alkyleneradicals, it may contain one to 10 carbon atoms, may be straight orbranched and may bear substitutents, such as hydroxy, lower alkoxy,carboxy or phenyl groups.

If the radical R represents optionally substituted alkyl, alkenyl orcycloalkyl radicals with five to l2 members in the carbocyclic ring, itmay bear substituents, such as hydroxy, lower alkoxy, carboxy,cyclohexyl, phenyl or sulfonic acid groups or 5-membered heterocyclicradicals with O or N- hetero atoms. The preferred cycloaliphaticradicals are the cyclohexyl radical and its derivatives having loweralkyl groups (methyl, ethyl).

If the radical R represents optionally substituted phenyl or naphthylradicals, it may bear substituents, such as hydroxy, lower alkoxy,carboxy, sulfonic acid, amidosulfonyl, anilidosulfonyl, trifluoromethylgroups or halogen.

If the radicals R and R jointly with the adjacent N atom, form aheterocyclic ring, the latter is a five, six or seven-member ring whichmay be substituted by lower alkyl or carboxy groups and which containsone N or one N and one 0 hetero atom.

In the radical v, W a

denoted Y, examples of groupsoffoi'mula 7 Rs CON which are of specialinterest are methyl-, ethyl-, n"-

propyl-, isopropyl-, n-butyl-, isobutyl-, tert.butyl-, N- amyl-,isoamyl-, n-hexyl, n-hepty|-, n-octyland 2- ethylhexylamino groups; thedimethyl-, diethyl-, diisopropyl-, di-n-propyland di-n-butylaminogroups; the allylamino group, the 2-hydroxyethyl-, 2-hydroxypropyl-,3-hydr0xypropyl-, l-hydroxybutyl-2-, lhydroxy-2-methylpropyl-2-aminogroups; the bis-(2- hydroxyethyl)-, bis-(2-hydroxypropyl)-amino groups;the N-methyl-N-2-hydroxyethyl-, N-ethyl-N-2-hydroxyethyland,N-n-propyl-N-2-hydroxyethylamino groups; the 2-methoxyethyl-,2-ethoxyethyl-, 3- methoxypropyl-, 3-ethoxypropyl-, 3-isopropoxypropyl-3-n-butoxypropyland, 4-methoxybutylamino groups; thebis-(2-ethoxyethyl)-amino, carboxymethylamino,N-methyl-N-carboxymethylamino, 2-carboxyethylamino, benzylamino,furfurylamino, N-methyl- N-benzylamino, cyclohexylamino,4-methylcyclohexylamino, N-methylN-cyclohexylamino and, N-ethyl-N-cyclohexylamino groups; the phenylamino, 2-, 3- or 4- methylphenylamino,2,4-, 2,5- or 2,6-dimethylphenylamino, 2,4,6-trimethylphenylamino, 2-,3- or 4- chlorophenylamino-, 2- or 4-methoxyor -ethoxyphenylamino, 3- or4-aminosulphonylphenylamino, 2- or 4- carboxyphenylamino and,4-hydroxy-3-carboxyphenylamino groups; the N-methyl-, N-ethyl-,N-isopropyl-, N-n-propylor N-n-butyl-N-phenylamino, N-ethyl-N-4-methylphenylamino, N-methyl-N-2-carboxyphenylamino,N-2-hydroxyethyl-N-phenylamino and, N-2-hydroxyethyl-N-3-methylphenylamino groups; the morpholino, piperidino,pyrrolidino or hexamethylenimino groups; the l-naphthylamino and 2-naphthylamino groups.

The SO H groups, the SO Z groups when present and also the reactiveradical may be bound to the radicals R, and R and to the radical R,when-the latter is aromatic. R and R may each contain not more than twoof the aforenamed groups, but R, may bear 1, 2 or even 3 of such groups,for example 2 -SO H groups on R and 1 reactive radical on R2,

or 1 SO Z group on R,, 2 --SO H groups on R, and

1 reactive radical on R or 1 SO H group on R,, one SO ,Z group on R,,, l

SO H group and l reactive radical on R or 1 SO H group on R one -SO Hgroup on R and l reactive radical on R or I -SO;,H group on each of R Rand R and l reactive radical on R, or 1 reactive radical and l -SO Hgroup on R and 2 SO H groups on R etc.

The reaction of the water-soluble dyes used as starting products with acompound of formula (III) is carried out preferably in aqueous medium.It may, however, be effected in an organic solvent or in a mixture oforganic solvent and water, which can be of special advantage if theintermediate is poorly soluble or insoluble in water. 1

Suitable organic solvents for this purpose include alcohols, acetone,benzene, toluene and tertiary organic bases such as pyridine. Thecompound of formula (Ill) can be employed as it is in concentrated formor in solution in an organic solvent. Highly suitable organic solventsare acetone, benzene, chlorobenzene and toluene.

The reaction temperature is adjusted to the reactivity of the startingproducts and varies from 0 to 30 C, the preferred temperature rangebeing l030 C.

The reaction is conducted in the neutral to weakly acid pH region of,e.g., pH seven to four. For neutralization of the equivalent of hydrogenfluoride which is formed, a buffer mixture, e.g., an acetateacetic acidmixture, is added to the solution at the commencement of the reaction,or an acid-binding agent is added in solid, pulverized form or inaqueous solution in the course of the reaction, suitable agents beingsodium or potasium carbonate, sodium and potassium hydroxide, calciumand barium hydroxide. The addition of small amounts of a wetting oremulsifying agent accelerates the reaction rate.

The reaction is controlled so that only one fluorine atom of thecompound of formula (III) reacts with an exchangeable hydrogen atom.

On completion of the condensation of coupling reaction the reactionsolution or suspension may, if desired, be neutralized, after which themetal complex dye formed is precipitated with sodium or potassiumchloride or acid, filtered off with suction, washed and dried undercontrolled condition.

As the new metal complex dues are highly reactive, it is advisable toadd to them, either before or after drying, a buffer salt or a mixtureof buffer salts which will maintain the pH value in the vicinity of theneutral point, e.g., in the pH region of five to seven, and so enhancetheir stability in storage as dry powders and in padding liquors orprinting pastes prior to application.

The water-soluble dyes of this invention which bear a radical of theformula (IV) are suitable for the exhaustion dyeing, pad dyeing andprinting of animal and vegetable fibers, regenerated cellulosic fibers,casein fibers, animalized cellulosic fibers, synthetic polyamide fibers,blends of the aforenamed fibers and leather. The dyeings, which, ifnecessary, may be submitted to an alkaline aftertreatment with heatingfollowed by soaping have good fastness to light, washing, milling andperspiration. The dyes are applicable by continuous and semi-continuousmethods, such as the pad-jig, pad-roll, pad-steam and thermofixationprocesses.

These new reactive dyes have good solubility in water, show goodcompatibility with salts and hard water and good reactivity with animal,vegetable and synthetic polyamide fibers. They reserve acetate,triacetate, polyester, poly'acrylonitrile, polyvinyl chloride, polyvinylacetate and polyalkylene fibers. Owing to their good solubility inwater, the unfixed proportion of the applied dye can be easily removedby washing from the dyed or printed goods.

The reactive dyes of this invention which bear only two sulphonic acidgroups are well suitable for the exhaustion dyeing of cellulosic fibersand for the acid dyeing of wool, silk and synthetic polyamide fibers.

The dyeings and prints obtained with these dyes are of particularly highquality because the dyes form a stable chemical linkage with the fibermolecule, which normally imparts outstandingly food fastness to wettreatments. If the entire amount of applied dye does not react with thefiber, the unreacted amount can be cleared from the substrate by washingoff and, if necessary, soaping, with heating to high temperatures asrequired. For this purpose synthetic detergents can be used, e.g.,alkylaryl sulphonates (dodecylbenzene sulphonate), sodium lauryl, cetylor oleylsulphate, sodium laurylpolyglycolether sulphates, monoalkylanddialkyl-phenylpolyglycol ethers, if desired in conjunction with sodiumpolyphosphate.

The dyed, padded or printed dyes are fixed on the fiber in the dyebathor in a fresh medium, if required after intermediate drying. If a freshbath is used it is advisable to fix in the presence of a water-solublesalt, eg sodium sulphate, to prevent partial re-dissolving of the dye inthe medium. Fixation of the dye radical on the fiber can be effectedwith heating, e.g., in steam or in dry heat as in the thermofixationprocess, or alternatively by storage at room temperature or atmoderately high temperatures.

The optimum conditions of application for the dyes vary widely with thenature of the fiber. In exhaustion dyeing, padding and printingprocesses they are applied to animal and synthetic polyamide fiberspreferably from an acid, neutral or weakly alkaline medium, e.g., in thepresence of acetic, formic, sulphuric or oxalic acid, ammonium sulphate,sodium acetate, sodium bicarbonate, sodium or potassium carbonate,sodium metaphosphate, trimethylamine, pyridine, quinoline, etc. Dyeingcan be carried out in an acetic acid to neutral bath in the presence oflevelling agents, e.g., polyoxethylated fatty amines, or mixtures ofthese and alkylphenyl or alkylpolyglycolethers, and the bath adjusted toa neutral or weakly alkaline reaction at the end of dyeing by theaddition of small amounts of an agent of alkaline reaction, e.g.,ammonia, sodium carbonate or bicarbonate, or a compound which reactsalkaline on heating, e.g., hexamethylene tetramine. Subsequently thegoods are well rinsed and if necessary acidified with acetic acid.

The exhaustion or pad dyeing and the printing of cellulosic fibers withthe new dyes is best carried out in alkaline medium, e.g., in thepresence of sodium carbonate or bicarbonate, caustic soda or causticpotash solution, calcium hydroxide, sodium metasilicate, sodium borate,water glass, trisodium phosphate, ammonia, trimethylamine, quaternarybases, e.g., tetra-alkylammonium compounds. To prevent reductivereactions in dyeing, padding or printing, it is often of advantage toadd a mild oxidizing agent, such as sodium 1- nitrobenzene-3-sulphonate.Fixation on cellulosic as on other fibers can be accomplished withheating. However, given the use of moderately strong alkalis, such assodium or potassium carbonate, the dyes can be applied in the cold, withfixation in a saturated sodium chloride or sulphate solution containingsodium carbonate, or by storage at room temperature. Fixation isfollowed by thorough rinsing and soaping to remove the unfixedproportion of dye. Stronger alkalis, such as sodium hydroxide andtrisodium phosphate, can of course be used but, as they increase thereactivity with the fiber, there is a greater danger of hydrolysis forthe proportion of dye not reacted with the substrate.

In comparison with the next comparable dye of French Pat. 1,330,585 andBritish Pat. 1,022,043 the dyes produced in accordance with the presentinvention exhibit a higher degree of reactivity.

In the following Examples the parts and percentages are by weight andthe temperatures are expressed in degrees centigrade.

Example 1 85.8 Parts of the copper complex compound of l-(2'-hydroxy-4-sulpho-6'-aminonaphthyl)-5-(2"-hydroxy-5"-sulphophenyl)-3-for:mazyl-carboxylic acid-(6"'-sulphonaphthyl-l"'-amide) in the form of the trisodium salt aredissolved in 550 parts of water. The solution is adjusted to pH 5.0 with30 percent acetic acid and clarified by filtration, on which it is runinto a reaction vessel fitted with a reflux condenser. 32 Parts ofcrystallized sodium acetate are added, followed by sodium carbonate tobring the pH to 6.0. Eighteen Parts of2,4,6-trifluoro-5-chloropyrimidine are added within 2 hours at l020 withstirring and with the controlled addition of dilute sodium carbonatesolution to maintain the pH value in the range of 6.0 to 6.5.Subsequently stirring is continued at l020 until no further free aminogroups are indicated. The reactive dye formed is then salted out withsodium chloride, filtered off, washed with aqueous sodium chloridesolution and carefully dried with vacuum. On grinding it is obtained asa dark powder which dissolves in water to give green-blue solutions.This new dye is the copper complex of the formazane of the formula or,more exactly, a tautomeric form of this formazane. The aminoformazanedye employed in this reaction can be prepared by coupling diazotizedl-amino-2-hydroxy-6-nitronaphthalene-4-sulphonic acid with the hydrazoneof glyoxylic acid-(6-sulpho)-naphthylamide and2-hydroxy-l-hydrazinobenzene-S-sulphonic acid in the presence of acopper-yielding agent to yield the copper complex compound ofl-(2'-hydroxy-4'- sulp ho-6'-nitronaphthyl)-5-(2-hydroxy-5"-sulphophenyl)-3-formazylcarboxylic acid-6"- sulphonaphthyl-l "-amide) inthe form of the trisodium salt. 88.8 Parts of this salt are dissolved in500 parts of water at 65, 17 parts of anhydrous sodium sulphide areadded and the solution is stirred at 65 until reduction is complete. Theaminoformazane dye can be salted out and isolated, or alternativelyemployed in the dissolved form.

Example of Application in Pad Dyeing A mercerized, bleached cottonfabric is padded with a liquor containing 2 percent of the dye ofExample 1, 1 percent sodium sulphate and 0.3 percent sodium carbonate,expressed to retain 70 percent of its weight of the liquid, rolled upand the roll lapped in plastic sheet to exclude air and so preventpartial drying at the edges. The dye solution and the solution of sodiumcarbonate and sodium sulphate are prepared separately and blendedimmediately before padding, preferably by means of an automatic mixingdevice. The roll of fabric is stored for 6 hours at 20-3 and afterwardsis rinsed with cold and hot water, soaped for 20 minutes at the boilwith a solution of 2 parts of a non-ionic detergent in 1,000 parts ofwater, rinsed again and dried. A green-blue dyeing is obtained which isfast to washing and water.

The nickel-containing reactive formazane dye produced in an analogousmanner, on application to cotton fabric by padding, gives a dyeing ofcomparable fastness but with a slightly less greenish shade.

Example of Application in Printing A cotton sateen fabric is printedwith a paste prepared with 40 parts of the dye of Example 1 100 parts ofurea 380 parts of water 450 parts of 4 percent sodium alginatethickening parts of sodium l-nitrobenzene-3-sulphonate parts ofanhydrous sodium carbonate 1,000 parts Example of Application inExhaustion Dyeing Two parts of the dye of Example 1 are dissolved in4,000 parts of cold water and the solution raised to on which two partsof 100 percent acetic acid and three parts of a mixture of apolyoxethylated fatty amine and an alkylpolyglycolether are added. intothis dyebath are entered 100 parts of a wool fabric. The bath is broughtto the boil in 10-20 minutes and held at the boil for -60 minutes.Subsequently about three parts of 25 percent ammonia and three parts ofhexamethylenetetramine tetramine are added at -90 and treatment iscontinued for 20 minutes at The dyed fabric is rinsed thoroughly, withsome acetic acid added to one change of rinsing water, and dried. Alevel green-blue dyeing is obtained which is fast to washing,perspiration, water and milling.

In the following table further metal complexes of formazane dyesconforming to the present invention are specified. In the metal-freeform they have the general formula and in the table they aredistinguished by the significance of the symbols Y and X, by the metalused for complex formation fastness to light and wet treatments. 35 andby the shade of the dyeing on cotton.

W 7 7' I I TABLE OH OH Ex. I Shade on No. A B Y X Metal cotton 2 OH OHCON(C:H5)2 Cl Cu Navy-blue.

I l S 03H S 03H Cu Do. (1 011 D0.

5 OH do Cl Cu D0.

- -C ONE- OzN l S 03H 6 Same as above do Same as above F Cu Do. 7.- "dod0 "do CH; CH D0.

8. (I)H d0 -CONH(CH )3OCH1 C1 C11 D0.

i CH3 9 0H do C H Cl Ni Grey-violet.

Cl CONHCHzCH-C4H9 SOaH TABLE-Contiuued 01-1 0H Ex. I I Shade On No. A BY X Metal cotton 10 '.'d'5'.'; II. .I. A EBJH 01 Cu Grey- H03s- CONH--OH 11 OH OH -coNHcH,cH,oH 01 Cu -w p,

HOaS- @s0m I l SOaH 12 ameasabove Same asabove Sameasabove H C11 D0- 13.0H H 01 Cu Do.

I c0NH- H SOaH SO|H 14 O H O H G1 On Navy-blue.

v CONHCH --C HOaS- I i c1 SOBH 0H 0H CONHC5H11(I1) 01 on HOaS-O 16 OH OH7 T51 11 01 Cu D0.

HOOC O OSO3H -0 ON-C l SO H 17 0H OH /j 01 Cu D0.

CO-N H 0 HOaS- I l SOaH $03K 18 0H Sameasabove CON(C2H4OH) .4 01 Cu Do-I som 19 'OH 50 11 H 011 'D TABLE-Continued OH OH Ex. I I Shade on No. AB Y X Metal cotton 20 OH 0H 01 Cu Grey-blue.

CONH-OS 0mm HOa'S- I I S 0 H 01 21 ()H OH OGH3 v C1 Cu D0 HO3S- SO H-CONH-C I I Cl 2 (|)H Same as above C1 C1 Cu Grey-violet.

I CONHQSO3H I S OgNHCHg 23 (|)H 11 s 0 H C1 Cu Blue.

I c1 CONH 24 0H CH C1 Cu B1ue.violet.

I I I -OONH O O -s 0111 I I S 5H 2 z b)2 25 Same as above Same as aboveSame as above F Cu D0 26. 11 OH 15 0 H G1 On Do 0 I O [I) I I S OaH S03H 27 (')H ([311 S|O H 01 Cu DO.

O O C ONE-8 I I I S OzNH- NO; S 0 H 28 OH OH Br Cu Navy-blue.

I I CONH I I S 03H S 03H Same as above Same as above Same as above CI CuD 30.4... 011 do V w Cl Cu 170- TABLE-Continued OH OH Ex. I I Shade onNo. A B Y X Metal cotton 31 OH OH CI Cu Green.

I 0 ON H HO: 5-8 s 03H 32 OH OIH C1 Cu N avy-blue.

HO; S S 03H I I S 0 H S 0 H as 0H Same as above 0x Cu Grey-blue.

O ONH- I al 34 OH OH 01 Cu Olive-grey.

C ONH- S OaH S OaH I H: N 2

35 CIJH ()H I 01 Cu Navy blue.

0 O NH CHaC 0-HN Cl I I S 0 H S OaH as ([)H ?H ?O H 01 Cu Grey-violet.

- C O-NI-I- I I S OzNHs S OzNHz S 0 H I 37 (In! (|)H H C1 Cu Navy-blue.

H O3SU U I I C H; S 0 1! 38 (I) II Same as above. II F Ni Violet-brown.

I S 0 H 39.. Same as above. do II C1 C11 Navy-blue.

40 (III (|)1[ --CONHC4Hq CI Cu DO- I IIO3S- -S 0.1"

TAB'LE c'ontmueii OH OH E I I Shade on No A B Y X Metal cotton 41. OH OHII CI Cu Grey-blue.

O-s 03H 42 OH 011 CI Cu Navy-b11112 IIOuS- I S 03H S 03H 43 OH OH I C!Cu Grey-blue CONH- Y S 0 H I s 03H CgH5O 44 OH OH O O-NH Cl NiGrey-violet.

l I I Br S 0 H S O:NH2 45 on 11 c O-NCHg-CH=CH2 01 Cu Navy-blue- }IO3S S0 H CH3-?CH3 46 Same as above 0H CONHC1ICOOII 01 Cu Do (1H CI'I(CH3)2 IS OaH 47 d0 Same as above -CONI-IC I ?H 0] Cu Do.

N O I l HN 48 "do d0 -CONII-CH -CII 7 CI Cu D0- NH N I 49 .do ..d0-CONHCH; I C1 Cu D0.

50 .d0 do C ONHCH 01 Cu D0- 51 "do do x. -GONCH;CH OH C1 C11 D0.

TABLE-Continued OII OH Ex. I I Shade on No. A B Y X Metal cotton 52 10.410 CONH (CH;) 01 Cu Do.

O-ClI(CHa)2 53 do do --CONHC(CH3)3 01 Cu D0- 54 do .Q. .do -COI?TH I 01Cu Do.

I a)a 55 db -.clo Cl Cu Do.

-CON-CH; JH1COCH 56 do do 01 Cu Do.

CON

57 ..do do 01 Cu D0. CON

ss--' OH OH 01 cu Blue-violet.

| CO1 II- I CH S 03H l 1 I S 03H S 07-CH(CH5)2 69 Same as above OH H 01Cu Navy-blue.

- CON C1 NHGO I CH3 0 I (EH5 SOJH 60 -do CH C O NHCH -([3 H1 C1 C11Blue-violet.

| SOrNII I SOaH 61 OH OH CONHCH 0! Cu Navy-blue.

Same as above -CONHC H Cu Do. do.. CON(CH3) Cu Do. -do- -CONHCH;C Cu Do.do CONHCHCHCH3 01 Cu D0.

66 d0 do -CON(CH;CHCH3) C1 C11 67 ..d0 (1o CONCH CH;OH Cl Cu 0- 68 .-d0.do -CONHCH COOH C1 C11 69 d0 ,d0 CONOH COOH C1 C11 0- TABLE-ContinuedOH OH Ex. I I Shade on No. A B Y X Metal cotton 70 OH -do CON(C H 11) 01Cu D0.

HOzS

I S 01H 71 Same as above do 01 C 1 D -CONH 72 ..d0 do 01 Cu Do.

0 ON-- OCzHs JH:

73 -.d0 .do 01 Cu D -C ONH- H CH:

74 "do .do 01 Cu 1m 0 OI-II H E HO-CHCH3 75 ..do .do Cl Cu Do.

-0 ON-CH2C|3H 01 Cu Do. C 01? H E CH2COOH 01 Cu Do. C ONH- H OHCONHCmHz| Cl Cu D0. CONHCH(CH2)10CH2 Cl Cu D0.

80 ..do do CI Cu D0.

CONH(CHz)4 H 81 do n do -CONHCH(CH )5CH, Cl Cu Do.

82 ..do do --CONHC!3HCOOII Cl Cu D0.

(CHzhCOOH 83 do do COI@COOH 01 Cu Do.

84 ..do ..d0

CON H CaH-l Cl Cu D0.

85 -do do (3H C! On D0 86 do d0 Cl Cu Do.

CONH Br 87 d0 do Cl Cu D0.

-CONHC CH3 88 V "(1Q d 01 Cu DO- -c O-NH-Q 89 "d do G 01 Cu Do.

TABLE-Contlnued OH OH Ex. I Shade on No A B Y X Metal cotton 90".. OH HCH; 01 Cu Do.

HOaS O O--NH- CH:

| S 0311 S 03H 91... Same as above Same as above. CH; 01 Cu D0.

0 ONH- 92 "d0 (|)H C ONH-CzH4- S 03H C1 011' D0- HOa S- 93 -.do Same asabove (I311; Cl Cu D0- --C O--N-CZH4 S 03H formulas of representativedyes of the foregoing Exam- Example 18 ples are as follows:

The copper complex compound of.the formula Example 8 The copper complexcompound of the.formula I SO II SOaIl F The copper complex compound ofthe formula The copper complex compound of the formula on n! N HolsN=NCH=NNH --NH 17F 01 \OgH SOaH Example 42 The copper complex compoundof the formula We Claim. 3. The complex, accordingto claim 1, of copperand v 1. A complex of copper and a compound of the fora compound offormula mula H N OH OH N=N(l3=N-NH NH T4 60 O-N N NH /N F l N I igwmnoom I I =0 soan soan 1 Ill 01 808E SO'H l 4. The complex accordingto claim 1, of copper and a compound offormula I OH OH A wherein l l NN= C=NNH NH T11 01 /N- N(C:H|OH):| I R: SO|H 03H F 5. The complexaccording to claim 1, of copper and a is N,N-diethylamino,N-S-methoxypropylamino, compmmd f formula N,N-di-(2-hydroxyethyl)aminoor N-phenylamino.

OH 7 7 "OH 2. The complex, according to claim 1, of copper and acompound of formula Hogs NH W 7 WM 01 L 011" OH 0 I N S0111 01K F-N=NC[=N-NH NH T4 I 01 N NH N(C:H5)2 X SOQH 302E F UNITED STATES PATENTOFFICE QERTIFICATE OF CORRECTION- Patent No. 3'. 725 382 Dated Anril 31973 Inventm-(S) Philippe Grandjean It is certified that error appearsin the above-identified patent m: said Letters Patent are herebycorrected as shown below:

Column 2 line 16,

add SO2NHC2H4OIH after I CH3 I I Column 2 line 19 I I h I I I I I Idelete IS0 NHC H och Column 2 line 37 l I I I I delete "alkylene" andinsert therefor ---alkehyl---'.

Column 2 line 63 delete 3 n R and insert therefor 3 -CO- v o I I 4 vFORM "$69) I uscoMM-oc scan-Pea UNITED STATES PATENT OFFICE CERTIFICATEOF CORRECTION Patent No. 3.725,382 Dated April 3, 1973 inventofls)Philippe Grandjean PAGE 2 "it is certifiedvthat error appears in theabove-identified patent and .a; said Letters Patent are hereby correctedas shown below:

Column 2 line 67,

delete R CON R and insert therefor Column 3 line 7,

delete the after lhydroxybutyl-2 and insert therefor and I C I Column 3line 9 delete the after hydroxyethyl)- and insert therefor -and-. I

Column 4 line 10,

delete "30 and insert therefore -20 lumn 5 line 1,

delete "food'? and insert therefor -good-.

FQBM 0 9- I usco -Dc wan-P99 fi u.s. sovzmmsm rnmmqa 01:"?! I!!! o-eu-au1 UNITED STATES PATENT OFFICE @ERTIFICATE OF CORRECTION Pate-m: NO.3,725,382 Dated April 3, 1973 7 PAGE 3,"

Iriventor(S) Philippe Grand-lean it: is certified that error appears inthe above-identified patent ls-11L said Letters Patent are herebycorrected as shown below:

Column 7 line -2 delete "liquid" and insert'therefor --1iquor.

Column 8 line 12 delete the word "tetram ine".

Column 7-8 example 8, Y A column,

delete and insert therefor so H FORM po-zvso (10-63) uscoM -pg:cda'ro-pqq w u.s. sovznumzur rpm-rm; orflgg': pig 0 360-3341.

33 a Dated p il 3, 1913 Patent No. 13

Inventor(s) PhilippeGfrandjean PAGE 4 g, 1 It: is-certified that? errorappears in the above-identified patent and that seidLetgslPatEent arehereby corrected as shown below:

Column 9-10, B column,

'delete and insert fihrefo: OH

UNITED STATES PATENT OFFICE- CERTIFICATEOF CORRECTION- Patent No.3725382" Dated April 1973 G lnventm-(s) Phlllppe Grand ean A L 5 It iscertified that error appears in the above-identified patent that saidLetters Patent are hereby corrected as shown below:

0H Column 9-10, example 13, B column,

delete and insert UNITED STATES PATENT OFFICER CERTIFICATE OF CORRECTIONPatent 3,725,382 Dated April 3; 1973 Inventor(s) Philippe Grandjea'nPAGE 6 "it is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

. OH Column 11-12, example 24, B column,

delete II II z z s 2 and insert therefor SOZN (CZHS) 2 7 Column 11,example 27, shade on cotton (column;

delete "Do." and insert therefor --greyblLie'-. Column 22, line 41delete "37" andinsert therefor --39--.

F or-m 0 1050 (10-69) UsCOMM-Dq 608 76-P69 1: us. eovznnnzn-r PRINTINGorrlc; jg 0-in-3.

UNITED STATES PATENT OFFICE e QERTIFICATE OF CORRECTION Patent No-3,725; 382 v Q Dated April 3, 1973 d 4'- Inventor(s) 'p'h- 1 Grandj eanIIAQL 7 It is certified that error appears in the shove-identifiedpatent end the": said Letters Patent are hereby corrected as shownbelow:

Column '23, line 14, claim 1,

- insert I or the compound of the formula OH I I 7 H I I, I. i (If WWI:

Column 23, line 22,

delete the after."methoxypropylamin fi and insert I therefbi -o r- I iColumn 23, line. 23,

delete "er tI-phehylaminp" Column 23, line 25 insert the word -'theafter'...a compound of FORM P0 1051, (10-69) I 2 USCOMM-DC scan-Poo I #1 U.S. GOVFRNMENT PRINTING OFFKE "I, O-{il-lll.

2. The complex, according to claim 1, of copper and a compound offormula
 3. The complex, according to claim 1, of copper and a compoundof formula
 4. The complex according to claim 1, of copper and a compoundof formula
 5. The complex according to claim 1, of copper and a compoundof formula